Process for completely regenerating contaminated solutizer solutions



1943- R. w. M OMIE ETAL PRQCESS FOR COMPLETELY REGENERATING CONTAMINATED SOLUTIZER SOLUTION Filed May 28, 1941 lxcc r l nvenforst Rulon Wells McOnHie' Orris L. Davis Alan C. Nyxon 59 Their Afforneg Ly: E mccuconpqu 3 2330 E58 E E ES UNITED STATES PATENT OFFICE PROCESS FOR COMPLETELY REGENERAT- {ggNgONTAMINATED SOLUTIZER SOLU- Rulon Wells McOmie, Martinez, Orris L. Davis,

- Oakland, and Alan C. Nixon, San Francisco, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of. Delaware Application May 28, 1941, Serial No. 395,506

15 Claims. (Cl. 252-192) This invention relates to the art of refining hytively stable emulsions with the hydrocarbon oil drocarbons by extraction with so-called solutizer under treatment, probably due to gradual acsolutions, and more particularly to a process for cumulation of emulsifier believed to be resinous regenerating solutizer solution. Specifically, it substances not removable by steam stripping, is concerned with a process for treating contamiwhich emulsions either reduce the throughput nated solutizer solution to remove solids and due to retardedsettling or cause. carry-over oi resinous emulsifiers which have accumulatcd-=in..,. valuable solutizer. ,f said solution during its use, whereby the solution """Iheexact source and che'ii'iic'alcoi'nposltion oi .is completely regenerated. the emulsifier are not known. It appears to be The solutizer process by means of which mer- ,a gummy materialoi a resinous nature. Possible captans and other weak organic acids contained sources of it include cracked gasolin f ds in Sour hydrocarbon distillates, and more partaining dissolved gums, oxidation of small ticularly in gasoline distillates, are extracted with amounts of cracked gasoline dissolved in the sosoiutizer solution, i. e., aqueous solutions of alkali lution and oxidation of portions or solutizer sometal hydroxides containing solutizers, is well lution, such as alkyl phenols which may purknown. The solutizer process has been described, posely form part of the solutizer solution or which and the several compounds particularly suitable may accumulate in solutizer solutions when as solutizers have been enumerated in a series of cracked gasoline feeds are treated. patents and patent applications, as well as in the Various expedients have been suggested, some general literature, for example, in the Yabroff more useful than others, to serve as an aid to and et al. U. S. Patents 2,149,379, 2,149,380, 2,152,166, in addition to steam stripping, to obviate the 2,152,720, 2,152,723, 2,164,851, 2,186,398, 2,202,039, emulsification and foaming diificulties. They in- 2,223,798, 2,229,995; Refiner and Natural Gasoline clude changing the composition of the solutizer Manufacture, May, 1939, pages 171 to 176,- and solution so as to decrease its tendency to emulsify March, 1940, pages 73 to 76; Industrial and Enwhen contacted with gasoline, for example, by gineering Chemistry, vol. 32, pages 257to262 (Febadding thereto various deemulsiflers, and means ruary, 1940); Chemical and Metallurgical Enand agents for cleansing o'r reconditioning the gineering, vol. 47, pages 776 to 778 (November, solution at various intervals.

1940); Oil and Gas Journal, vol. 39, No; 26, pages The first classof expedients mentioned above, 45 to 46 (November 7, 1940), etc. namely, addition agents, have not always proved The more desirable substances capable of actsatisfactory. In some cases, though they may ing as solutizers being relatively expensive, it be 'efiective in the beginning, their effect is short sometimes becomes necessary that the solution be lived, and they must be added in ever increasing regenerated and used over and over to obtain quantity, until finally such procedure becomes the maximum operating economy. impracticable.

- In the ordinary course Of treatment in a solu- Means and agents for cleansing the solution intizer p the r ener tion of solutizer solution clude among others solid adsorbents and soluis carried out by steam stripping. The fat solutions, to adsorb or precipitate the emulsifying tizer solution containing mercaptans and other 40 material. The main difliculty with this type of weak acids extracted from sour hydrocarbon distreatment i that only solutions which are relatillate is subjected to steam stripping in a contintively lightly Contaminated can be clean ed eflecuous regeneration to result in a lean solution of tively, and therefore, where the rate of con'tamb reduced content of mercaptans and weak acids, nation is high, the i p e t o be g d 1 and ready to be recirculated to contact more insoon dissipated when treatment is resumed. coming sour gasoline. The object of this invention is to facilitate the Even though it may be possible theoretically treatment of hydrocarbon distillates by means of to use asolutizer solution indefinitely by continusolutizer solutions. Another purpose is to deally regenerating it by steam stripping, this crease the costs of operation in solutizer plants method results in certain difliculties. Experience by minimizing or preventing losses of valuable has shown that despite carefully conducted steam solutizer which are suffered when contaminated stripping, it is not possible to remove all the unsolutions must be discarded. Still another purdesirable substances which may accumulate in pose is to decrease emulsion and foaming did!- the solution during the treatment. culties in solutizer plants. A more particular pur- Solutions used a long time tend to form relapose is to provide a process for completely regencrating used solutizer solutions, particularly those containing accumulated emulsifiers.

Our invention is based on the discovery that a used solutizer solution may be completely regenerated by subjecting it to a process which removes all the emulsifying material in it, thus making it possible to produce a solution which has substantially the same composition and properties as the original solutizer solution, said solution being again suitable for use in the solutizer process for the extraction f mercaptans.

Our process consists essentially of the following five main steps:

1) Neutralizing the contaminated solutizer solution with CO2 to produce a carbonated liquid, thereby precipitating the emulsifier and other impurities as solids and, if alkyl phenols are present, liberating them, whereby a separate oily phase is produced. I

(2) Removing the solids, including the emulsifier, from the carbonated liquid.

(3) Recausticizing the carbonated liquid with lime. If an oily phase is present, it may be separated to be discarded or to receive a purification treatment, in which case the aqueous phase may be recausticized alone.

(4) Reconcentrating the recausticized liquid.

(5) If necessary, adding back any solutizer lost, for example in reconcentrating, or discarded with the separated oily phase.

Instead of using lime for recausticizing, we may use metal oxides which are at least slightly soluble in water and whose metal carbonates are substantially insoluble, such as the dioxides of Ba, Sn, and Li.

By a contaminated solutizer solution, we mean one containing an emulsifier which has slowly ac 'cumulated during the steam regeneration treatment and which is in solution of colloidally dispersed, thereby causing said solution to have a tendency to form emulsions which may be relatively stable when it is mixed with gasoline in the course of the treatment or to foam excessively when the spent solution is being stripped, thereby hampering the smooth operation of a solutizer plant, or both. v

In .order to facilitate the neutralization with CO2 and to make possible later recausticizing, the contaminated solutizer solution is usually first diluted with water, preferably distilled water. solutizer solutions, after having been steam stripped, normally are at least about 2 normal with respect to alkali metal hydroxide. At the time the solution is neutralized with C02 it should contain alkali metal hydroxide in a concentration preferably not greater than 1.5N. Thus when different 'layers.

starting out with a solutizer solution which contains alkali metal hydroxide in concentration of about 6N as is most usually used, it is desirable to carry out any neutralization in a dilution of at least 3:1 distilled water to solutizer solution.

The neutralization with CO2 is advantageously carried out by bubbling CO2 into the diluted solution in a manner which will insure the highest rate of absorption. A conventional type carbonating tower containing bailles, bubble plates or other contact means is to be recommended, as are any other advantageous arrangements for dis tribution of the gas throughout the liquid, such as spiders and the like.

The contaminated solutizer solution should be neutralized with CO2 to a pH value of 11 or below, and preferably about 10. At pH 10, the resinous emulsifier is precipitated as solids and any alkyl phenols present are liberated. As a result,

at least two layers are formed, one of which is an aqueous layer. If alkyl phenols are present, they form an upper oily layer in which the emulsifier and some of the other troublesome solids are dispersed. If alkyl phenols are absent, the emulsifier and other troublesome solids may form a layor which floats on the surface of the aqueous layer, or may remain dispersed in the aqueous phase, depending, among other factors, on their relative specific gravities.

The removal of the solids can be efiected by filtering, and in some cases by settling or centrifuging, etc., and may be carried out in any convenient and conventional manner.

After the solids have been removed, all of the carbonated liquid comprising an aqueous phase may be recausticized, or any oily phase, if present, may be first separated and the aqueous phase may alone be recausticized. The latter method will be preferred when the oily layer is known to contain dissolved undesirable material.

The two layers may be separated by simple decantation consisting of separately drawing off the For this operation a conventional type of separating apparatus will serve.

The lime used for recausticizing is best added as solid lime. Either slaked or unslaked lime is satisfactory, the latter being somewhat preferable. Better settling of the 08.00: formed and more complete recovery are to be had by adding the lime to the solution while hot, preferably at its boiling temperature or as close to it as is practical with the available equipment. The amount of lime to be added is determined by analyzing for carbonic acid. If carbonation has gone as far asthe bicarbonate, the, amount to be added should be approximately 5% to 10% in excess of the theoretical amount required by the equation: KHCO3+CaO=CaCQa+KOH.

After recausticizing, the solution and precipitate of CaCOa formed are separated and the supernatant liquid is removed.

To avoid any loss of KOH or potassium isobutyrate with the precipitate of CaCOs formed, the precipitate should be washed with water, and the resulting wash water be added to the separated recausticized solution. As aresult, starting out, for example, with a contaminated solutizer solution originally containing alkali metal hydroxide or alkali metal hydroxide and alkyl phenolate in a total concentration of about 6N, the recausticized solution and wash water may contain alkali metal hydroxide or alkali metal hydroxide and alkyl phenolate in a concentration of about .6N.

If desired, the recausticized solution may be given a treatment to remove minute quantities of Ca. Essentially this step consists of the addition of an equivalent amount of an acid or an alkali metal salt thereof, the Ca salt of which is completely insoluble in water, such as oxalic acid, phosphoric acid, etc., to precipitate the Ca as oxalate, phosphate, etc., as the case may be. This precipitation is best carried out in a hot solution. Oxalic acid is preferred because the solubility of its calcium salt does not decrease with tempera ture and hence has less tendency to deposit on the tubes of evaporator equipment.

The reconcentration of the solution is carried out by reboiling in any desired conventional manner.

not removed, these solids might in themselves stabilize emulsions if the solution were immediately used to treat hydrocarbon distillate.

An oily layer, if separated from the carbonated liquid, may be discarded, or subjected to a further treatment if it contains appreciable amounts of solutizer, e. g., alkyl phenols. This further treatment normally comprises a distillation to produce purified alkyl phenols and a pitch-like residue.

The final step of replacing any solutizer which may have been lost in the treatment will vary depending on the method of treatment employed. If the two phases of the carbonated liquid are not separated before recausticizing, only a very small amount f solutizer will be lost, and this is easily replaced ith fresh solutizer. If an oily phase containing solutizer is first separated, there are two sources of solutizer tobe added to the treated aqueous layer:

(1) The solutizer contained in the oily phase treated and purified as explained above.

(2) Fresh solutizer from an outside source.

The process is illustrated in the accompanying drawing which represents a simplified flow diagram of a preferred form.

For simplicity, the drawing does not show all pumps, heat exchangers, by-passes, vents, reboilers, and other auxiliaries; the proper placement of which will be evident at once to those skilled in the art. f,

Contaminated solutizer solution containing alkyl phenolates and resinous emulsifier is admitted from a source not shown through line I into dilution tank 2 where distilled water is added to it, from a source not shown, through line 3. After dilution, the solution is withdrawn through line 4 and conveyed -to carbonating tower 5, whence it runs downward over baffles, bubble plates, or other contact means in the tower in counter-current to carbon dioxide, or carbon dioxide mixed with inert gases, which is introduced at the bottom through line 6. Carbon dioxide is adsorbed, the emulsifier is precipitated, and alkyl phenols, if present, are liberated, forming an oily phase. Non-adsorbed gas leaves the tower through vent line I, and carbonated solution passes through line 8 to filter 9, where solids, including the emulsifier, are removed and dropped out through line H).

After the filtration, the solid-free liquid may be treated by alternative methods. It may be directly recausticized, or'in the case of the existence of two liquid phases, they may be first separated, each to receive a different treatment. If

it 'is found that the oily phase of thefiltered liquid contains dissolved undesirable material, preliminary separation is desirable.

If the filtered liquid is to be treated without first separating an ,oily phase, it leaves filter 9 through line l2 and is transferred to agitator 20 where it is recausticized with lime added from hopper 2|. The resulting mixture is stirred 'by an appropriate stirrer mechanism to precipitate CaCOs. The latter is allowed to settle and supernatant liquid is transferred through line 23 to tank or agitator 24. The precipitate in agitator 20 is washed with water introduced through 28 to be reconcentrated, or if desired, steps ma first be taken to remove small amounts of ca cium remaining in the solution.

If the latter steps be found necessary, oxal acid from hopper 35 is added to the dilute recau: -ticized aqueous solution contained in tank 24 i an amount just sufilcient to precipitate any sma amount of calcium remaining. The precipitate calcium oxalate is allowed to settle and is I( moved through bottom line 25 and the calciurr free solution is led to still 28 through line 26.

In still 28 the dilute solution is reconcentrate by reboiling, water leaving overhead through vs por llne21 and concentrated solution being with drawn through line 29 to settling tank 30, wher it is allowed to settle forsome time to re'mot the comparatively small amount of solid mate rial, chiefly Ca salts, which are precipitated dur ing the reconcentration step. The clear solutio is conveyed through line 3| to mixing tank 3 and the settled solid is removed through bottol line 32.

If two liquid phases are to be separated befoi recausticization, the filtered liquid is transferre from filter 9 through line I l to separator l3, whei the oily phase is allowed to rise to the top the aqueous phase, and the two phases are sepa rately and successively withdrawn through line l4 and I5, each to receive its further treatmer to be presently described.

First to be withdrawn is the aqueous phas which leaves separator l3 through line l4 an is led to agitator 20 where it is recausticized i substantially the same manner as has been pre viously described for the filtered liquid which we not first separated into two phases.

The oily layer in separator I3 is withdraw; and may be discarded, through line 31, or else i passed through line I5-and led to still l6, equippe with heater 38, where it is purified by distilla tion. The portion comprising the purified prod uct leaves still l6 overhead through line I8, an

in counter-current flow through an extractioi tower in which the aqueous phase is continuou: an emulsion of the oil in water type may b formed-which collects at the top of the solutize solution. A similar type of emulsion can b formed by stirring solutizer solution and gasolin together, and a stirrer test was accordingly de "vised whereby small amounts of solutizer solu line I9, and the wash water passes through line may be conveyed through line 26 directly to still tion and gasoline could be caused to form a1 emulsion under controlled conditions, and th time of settling measured.

(1) A full range cracked gasoline was stirrer vigorously with a contaminated aqueous solutize solut on containing potassium hydroxide 6N potassium isobutyrate 1.5N, and potassium phe nolate 1.0N under standard conditions. The set tling time (time necessary for separation of th two phases) was 3 hours with a rag. Anothe:

ce htrated. This treated portion containing potassium hydroxide 6.4N, potassium isobutyratt 1.45N, and potassium phenolate was then stirrer with the same full range cracked gasoline, ant

the settling time was found to have dropped in W minutes and twenty seconds. The solutions eparated cleanly and no rag remained.

(2) In another experiment a portion of the :ontaminated solutizer solution was diluted with vater, neutralized with CO2, filtered, and the iqueous phase was separated, recausticized with ime and reconcentrated. To thereconcentrated iqueous phase alkyl phenols were added in an lmount equal to that which had been removed vith the separated oily phase. This solution was hen stirred with a full range cracked gasoline, and the settling time in this case was reduced to 'our minutes and twelve seconds with a clean ireak.

We claim as our invention:

1. In a process for purifying aqueous alkali netal hydroxide solution containing an organic solubility promoter for mercaptans and a resin- )us emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with ;ald solution and regenerating the resulting spent solution, the steps comprising neutralizing said solution with CO2. to produce a carbonated lquid, thereby selectively precipitating the :mulsifier and other impurities as solids, removing'said' solids, and recausticizing at least a portion of the carbonated liquid.

2. The process of claim 1 wherein the concen- ;ration of the alkali metal hydroxide solution is Jetween 2.5 and .5 normal.

3. The process of claim 1 wherein the carbonited liquid is reeausticized with lime.

4. In a process for purifying aqueous alkali netal hydroxide solution containing an organic aolubility promoter for mercaptans and a resin- )us emulsifier accumulated in the course of re- Jeatedly treating hydrocarbon distillates with said solution and regenerating the resulting ;pent solution, the steps comprising diluting said solution with water, neutralizing the solution with CO2 to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other .mpurities as solids, removingsaid solids, recausaicizing at least a portion of the carbonated liqlid, and then reconcentrating.

5. The process of claim 4 wherein the water of dilution is distilled water.

6. The process of claim iwherein the alkali metal hydroxide content of the concentrated solution is above 2.5N, and that of the diluted solution is between 2.5 and .5N.

'7. The process of claim 4 wherein the alkali metal hydroxide concentration of the concentrated solution is about 6N, and that of the diluted solution is about 1.5N.

8. In a process for purifying aqueous alkali said solution with CO: to a pH of about 10 to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids, removing said solids, and recausticizing at least a portion of the carbonated liquid.

10. In a process for purifying aqueous alkali metal hydroxide solution containing an organic solubility promoter for mercaptans and a resinous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting spent solution, the steps comprising neutralizing said solution with CO2 to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids, removing said solids, and recausticizing at least a portion of the carbonated liquid with an amount of lime 5%-10% in excess of that equivalent to the amount of total carbonic acid in said carbonated solution.

11. In a process for purifying aqueous alkali metal hydroxide solution containing an organic solubility promoter for mercaptans and a resin- -ous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting spent solution, the steps comprising neutralizing said solution with COz to a pH of about 10, thereby converting said hydroxide to bicarbonate and selectively precipitating the emulsifier and other impurities as solids, removing said solids, and recausticizing at least a portion of the carbonated liquid with an equivalent amount of lime necessary to reconvert the bicarbonate to hydroxide.

12. In a process for purifying aqueous alkali metal hydroxide solution containing an organic solubility promoter for mercaptans and a resinous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting spent solution, the steps comprising neutralizing said solutionwith CO2 to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids. removing said solids, recausticizing at least a DOrtion of the carbonated liquid with lime and then treating said recausticized liquid with a small amount of an ionizable compound containing a radical the calcium salt of which is completely metal hydroxide solution containing an organic solubility promoter for mercaptans and a resinous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting spent solution, the steps comprising neutralizing said solution with CO2 to a pH of 11 or below to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids, removing said solids, and recausticizing at least a portion of the carbonated liquid.

9. In a process for purifying aqueous alkali metal hydroxide solution containing an organic solubility promoter for mercaptans and a resinous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting spent solution, the steps comprising neutralizing insoluble in water.

13. In a process for purifying aqueous alkali metal hydroxide solution containing an organic solubility promoter for mercaptans and a resinous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting spent solution, the steps comprising neutralizing said solution with CO2 to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids, removing said solids, recausticizing at least a portion of the carbonated liquid with lime and then treating said recausticizedf liquid with a small amount of an ionizable compound containing an oxalic acid radical.

14. In a, process for purifying aqueous alkali metal hydroxide solution containing a solubility promoter for mercaptans and a resinous emulsifier accumulated in the course of repeatedly treating hydrocarbon distillates with said solution and regenerating the resulting'spent solution, said promoter comprising phenolates, the

steps comprising neutralizing said solution with C0: to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids and forming two liquid phases, one an oily phase containing phenols and precipitated emulsifier dispersed therein, and the other an aqueous phase, removing said solids, separating said liquid phases, recausticizing the aqueous phase with lime, and returning at least a portion of the oily phase substantially free from emulsifier to the recausticized aqueous solution.

15. In a process for purifying aqueous alkali metal hydroxide solution containing a solubility promoter for mercaptans and a. resinous emulsifier accumulated in the course ofrepeatedly treating hydrocarbon distillates with said solusteps comprising neutralizing said solution with CO: to produce a carbonated liquid, thereby selectively precipitating the emulsifier and other impurities as solids and forming two liquid phases, one anoily phase containing the phenols and precipitated emulsifier dispersed therein, and the other an aqueous phase, removing said solids, separating said liquid phases, recausticizing the aqueous phase with lime, distilling the ofly phase to recover phenols and returning them to the re'causticized solution.

RULON WELLS 'McoMIE. ORRIS n DAVIS. ALAN c. mxoN. 

